This invention concerns water-soluble carbamate-functional materials and curable coating compositions containing such materials, especially waterborne coating compositions containing such materials.
Carbamate-functional materials have found particular utility in coating compositions as crosslinkable resins. Curable coating compositions utilizing carbamate-functional resins are described, for example, in U.S. Pat. Nos. 5,693,724, 5,693,723, 5,639,828, 5,512,639, 5,508,379, 5,451,656, 5,356,669, 5,336,566, and 5,532,061, each of which is incorporated herein by reference. These coating compositions can provide significant advantages over other coating compositions, such as hydroxy-functional acrylic/melamine coating compositions. For example, the coatings produced using carbamate-functional resins typically have excellent resistance to environmental etch (also called acid etch). Environmental etch results in spots or marks on or in the coating that often cannot be rubbed out.
One drawback of coatings with carbamate-functional resins is that they tend to require more organic solvent to achieve acceptable viscosity and for application. Carbamate-functional materials prepared from an isocyanurate of a diisocyanate, for example, are generally advantageous as an additive resin or principal resin in a coating composition, but these materials increase the viscosity of the coating composition so that more solvent is required. Coatings with higher amounts of organic solvent produce more regulated emissions during application.
Aqueous coating compositions have gained prominence due to the regulations on organic emissions. Such coatings have tended to be water-sensitive, however, because of the presence of the hydrophilic groups used to disperse the binder resins or surfactants, such as polyether-based surfactants, that remain in the coating film as low molecular weight, hydrophilic materials.
It would be advantageous to provide a water-soluble, carbamate-functional material for a coating composition that would not have water-sensitivity in a cured coating.
The invention provides a water-soluble, carbamate-functional materials and coating compositions, especially waterborne coating compositions, containing the carbamate-functional materials. The invention further provides a coating prepared from the coating composition and a coated substrate, especially an automotive substrate, having the coating thereon. The carbamate-functional materials of the invention have a sufficient number of xcex2-hydroxy carbamate groups to be soluble in water. The carbamate materials may be dissolved in water at ambient temperature or warm water, with the water being heated up to perhaps about 50xc2x0 C. The xcex2-hydroxy carbamate groups have the isomeric structures 
wherein each R is independently hydrogen, methyl, or ethyl and x is an integer of 1 to 3. Preferably, R is in each case a hydrogen and x is 1.
In one embodiment, the water-soluble, carbamate-functional materials may be represented by a structure
(Bxe2x80x94L"Parenclosest"nC 
in which B represents xcex2-hydroxy carbamate groups having the above structures; L represents a linking group formed by a hydrogen acceptor group; C represents an n-functional central moiety; and n is a positive integer. The carbamate groups are primary carbamate groups, i.e. there are two nitrogen hydrogens.
The central moiety C has up to about 5 carbon atoms per xcex2-hydroxy carbamate group, preferably up to about 4.5 carbons per xcex2-hydroxy carbamate group, more preferably up to about 4.0 carbons per xcex2-hydroxy carbamate group, and still more preferably up to about 3.0 carbons per xcex2-hydroxy carbamate group. In terms of the structure, the number of carbons of the C group may be represented by up to 5xc2x7n, preferably up to 4.5xc2x7n, more preferably up to 4.0xc2x7n, and still more preferably up to 3.0xc2x7n. For some applications, such as automotive topcoats, particularly automotive clearcoats, the C group is preferably aliphatic. In some preferred embodiments the C group includes an aliphatic ring.
The following description of the preferred embodiment(s) is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses.
In one embodiment, the water-soluble, carbamate-functional materials may be represented by a structure
(Bxe2x80x94L"Parenclosest"nC 
in which B represents xcex2-hydroxy carbamate groups having the structures 
wherein each R is independently hydrogen, methyl, or ethyl, preferably hydrogen and x is an integer of 1 to 3, preferably 1; L represents a linking group formed by a hydrogen acceptor group; C represents an n-functional central moiety; and n is a positive integer, preferably at least two.
Suitable examples of the linking group L include, without limitation, 
with one free bond of each group connected to B and the other free bond connected to C.
In one embodiment of the invention, the water-soluble, carbamate-functional material may be a homopolymer having a monomer unit represented by the structure 
in which each R2 is independently H or methyl and B is as defined above, or a monomer unit 
xe2x80x83in which B is as defined above.
The water-soluble carbamate-functional material may also be a copolymer having the monomer unit just described and having a fraction of different monomer units, particularly hydrophilic monomer units, in an amount so that the copolymer is water-soluble.
The xcex2-hydroxy carbamate polymer may be the polymerization product of a monomer prepared by reacting a glycidyl-group containing polymerizable monomer first with carbon dioxide to convert the oxirane group to a cyclic carbonate group, and then with ammonia or a primary amine to convert the cyclic carbonate group to a xcex2-hydroxy carbamate group. Examples of suitable oxirane group-containing polymerizable monomers include, without limitation, glycidyl acrylate, glycidyl methacrylate, glycidyl crotonate, and allyl glycidyl ether. Oxirane groups can be converted to carbamate groups by first converting to a cyclic carbonate group by reaction with CO2. This can be done at any pressure from atmospheric up to supercritical CO2 pressures, but is preferably under elevated pressure (e.g., 60-150 psi). The temperature for this reaction is preferably 60-150xc2x0 C. Useful catalysts include any that activate an oxirane ring, such as tertiary amine or quaternary salts (e.g., tetramethyl ammonium bromide), combinations of complex organotin halides and alkyl phosphonium halides (e.g., (CH3)3SnI, Bu4Snl, Bu4PI, and (CH3)4PI), potassium salts (e.g., K2CO3, KI) preferably in combination with crown ethers, tin octoate, calcium octoate, and the like.
The cyclic carbonate group is reacted with ammonia or a primary amine. The primary amine preferably has up to four carbons, e.g. methyl amine. Preferably, the cyclic carbonate is reacted with ammonia. The ammonia may be aqueous ammonia (i.e., NH4OH). The reaction ring-opens the cyclic carbonate to form a xcex2-hydroxy carbamate monomer.
The polymerization of the monomer preferably is carried out in water or in an a mixture that includes water. The xcex2-hydroxy carbamate monomer may be polymerized in the presence of free-radical initiators or with a redox initiator system. Useful initiators and redox initiator systems are well-known. The polymerization may be carried out without solvent or in an organic or aqueous medium. In a preferred embodiment, the xcex2-hydroxy carbamate monomer is polymerized in an aqueous medium, preferably without any organic solvent or with a minor amount (up to about 10% by weight of the aqueous medium) of a polar solvent such as methanol, tetrahydrofuran, propylene glycol monomethyl ether, or other water-soluble or water-miscible solvents. The xcex2-hydroxy carbamate monomer may be dissolved in water along with the initiating system and polymerized at a suitable temperature for the initiating system.
In an alternative embodiment, a homopolymer or copolymer including xcex2-hydroxy carbamate units may be prepared by including the corresponding cyclic carbonate monomer and forming the carbamate group from the carbonate group at some time during the polymerization of the corresponding cyclic carbonate monomer. For example, a primary amine or ammonia can be charged to the polymerization reactor and react with the cyclic carbonate group during the polymerization. The reactor can be pressurized for ammonia or a gaseous primary amine. The ammonia or primary amine could also be added during the polymerization reaction.
Examples of homopolymers and copolymers of the xcex2-hydroxy carbamate monomer useful for coating compositions are those that have weight average molecular weights of from about 5000 to over a million.
In another embodiment, the carbamate-functional compound of the invention may have a structure 
in which each of R1, R2, and R3 is independently 
wherein R is hydrogen, methyl, or ethyl.
This water-soluble xcex2-hydroxy carbamate compound may be prepared by reacting triglycidyl isocyanurate first with carbon dioxide to convert the oxirane groups to cyclic carbonate groups, and then with ammonia to convert the cyclic carbonate group to a xcex2-hydroxy carbamate group. The reactions proceed in the same way as for the monomer synthesis already described. Triglycidyl isocyanurate is commercially available or may be prepared by reaction of isocyanuric acid with an epihalohydrin, in particular epichlorohydrin.
In yet another embodiment, the water-soluble carbamate functional compound of the invention may have as C structures selected from alkylene groups having up to about six carbon atoms, especially butylene, pentylene, hexylene, and cyclohexylene; and 
Further examples of xcex2-hydroxy carbamate compounds of the invention may be prepared from glycidol carbonate, which has the structure 
by reacting the hydroxyl group with a compound having a functional group reactive with hydroxyl and then by reacting the product with ammonia to convert the cyclic carbonate group to a xcex2-hydroxy carbamate group. Glycidol carbonate is commercially available or may be prepared by reaction of glycidol with carbon dioxide, using such conditions as already described. Glycidol in turn may be prepared by reaction of allyl alcohol with peroxide. Alternatively, the alcohol group of one of the precursors to glycidol carbonate, either allyl alcohol or glycidol, may be reacted with the compound having a functional group reactive with hydroxyl before synthesis of the carbonate group and then carbamate group. This may be advantageous when the carbonate group may react with the compound having the functional group reactive with hydroxyl, for example if an esterification reaction is contemplated.
Examples of groups reactive with hydroxyl groups include, without limitation, acid groups, anhydride groups, isocyanate groups, lactones, oxirane (epoxide) groups, halides, and combinations of these. The reactions may be carried out under conditions typical for reactions of such groups with hydroxyl-functional compounds.
The allyl alcohol, glycidol, or glycidol carbonate may, for example, be reacted with a carboxylic acid-functional or anhydride-functional compound having up to about 5 carbon atoms per carboxylic acid group. Examples of suitable carboxylic acid and anhydride compounds include, without limitation, monocarboxylic acids such as butanoic acid; hydroxycarboxylic acids such as dimethylolpropionic acid; polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, alkyl-substituted phthalic, isophthalic, and terephthalic acids; maleic acid, fumaric acid, itaconic acid, malonic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and alkyl-substituted partially or fully hydrogenated phthalic, isophthalic, and terephthalic acids.
The esterification reaction can be conducted under typical esterification conditions, for example at temperatures from room temperature up to about 150xc2x0 C., and with catalysts such as, for example, calcium octoate, metal hydroxides like potassium hydroxide, Group I or Group II metals such as sodium or lithium, metal carbonates such as potassium carbonate or magnesium carbonate (which may be enhanced by use in combination with crown ethers), organometallic oxides and esters such as dibutyl tin oxide, stannous octoate, and calcium octoate, metal alkoxides such as sodium methoxide and aluminum tripropoxide, protic acids like sulfuric acid, or Ph4SbI. The reaction may also be conducted at room temperature with a polymer-supported catalyst such as Amerlyst-15(copyright) (available from Rohm and Haas) as described by R. Anand in Synthetic Communications, 24(19), 2743-47 (1994), the disclosure of which is incorporated herein by reference.
The allyl alcohol, glycidol, or glycidol carbonate may also be reacted with an isocyanate-functional compound. Examples of suitable isocyanate-functional compounds include, without limitation, monofunctional isocyanate compounds and polyisocyanates having up to about 5 carbons atoms per isocyanate group. Suitable examples of these include, without limitation, ethylene diisocyanate, 1,2-diisocyanatopropane, 1,3-diisocyanatopropane, 1,6-diisocyanatohexane (hexamethylene diisocyanate or HMDI), 1,4-butylene diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate, 1,4-methylene bis-(cyclohexyl isocyanate), isophorone diisocyanate (IPDI), the various isomers of tolylene diisocyanate, 4,4xe2x80x2-dibenzyl diisocyanate, and 1,2,4-benzene triisocyanate, the dimers and trimers of these (including biurets, allophanates, and isocyanurates), and so on.
The reaction of the allyl alcohol, glycidol, or glycidol carbonate with the isocyanate-functional compound can be conducted under typical conditions for forming urethanes, for example at temperatures from room temperature up to about 150xc2x0 C., and with catalysts such as, for example, tin catalysts including dibutyl tin dilaurate, dibutyl tin oxide, and the like.
The coating composition further includes at least one crosslinker reactive with functionality, preferably including the carbamate functionality, of the xcex2-hydroxy carbamate material. Particularly useful crosslinkers include, without limitation, materials having active methylol or methylalkoxy groups, such as aminoplast crosslinking agents or phenol/formaldehyde adducts. Examples of preferred curing agent compounds include, without limitation, melamine formaldehyde crosslinkers, including monomeric or polymeric melamine resin and partially or fully alkylated melamine resin, urea resins, and methylol ureas such as urea formaldehyde resin, alkoxy ureas such as butylated urea formaldehyde resin. Another suitable crosslinking agent is tris(alkoxy carbonylamino) triazine (available from Cytec Industries under the trademark TACT). Other useful crosslinkers include, without limitation, polyisocyanates and blocked polyisocyanates, curing agents that have siloxane groups, aldehyde groups, and anhydride groups. The curing agent may be combinations of these, particularly combinations that include aminoplast crosslinking agents. At least one crosslinker with functionality reactive with active hydrogens of the xcex2-hydroxy carbamate compound is included. Aminoplast resins such as melamine formaldehyde resins or urea formaldehyde resins are especially preferred. Water-soluble aminoplast resins for aqueous coating compositions are known. These include high imino-content melamine formaldehyde resins and fully methoxylated melamine formaldehyde resins.
In preferred embodiments, the crosslinker is at least about 5%, more preferably at least about 10% by weight of the nonvolatile vehicle. It is also preferred for the crosslinker to be up to about 40%, more preferably up to about 30% by weight of the nonvolatile vehicle. The crosslinker is preferably from about 5% to about 40%, more preferably from about 10% to about 35%, and still more preferably from about 15% to about 35% by weight of the nonvolatile vehicle.
The coating composition may include further crosslinkable compounds, resin, and/or polymers, preferably those that have active hydrogen functionality. Examples of additional compounds, resins, and/or polymers that may optionally be included are other carbamate- or hydroxyl-functional materials, including acrylic polymers, polyurethanes, and polyesters.
The coating composition used in the practice of the invention may include a catalyst to enhance the cure reaction. For example, when aminoplast compounds, especially monomeric melamines, are used as a curing agent, a strong acid catalyst may be utilized to enhance the cure reaction. Such catalysts are well-known in the art and include, without limitation, p-toluene sulfonic acid, dinonyinaphthalene disulfonic acid, dodecylbenzenesulfonic acid, phenyl acid phosphate, monobutyl maleate, butyl phosphate, and hydroxy phosphate ester. Strong acid catalysts are often blocked, e.g. with an amine. Other catalysts that may be useful in the composition of the invention include Lewis acids, zinc salts, and tin salts.
Although aqueous coating compositions that are free of regulated volatile organic compounds are preferred, a solvent may optionally be utilized in the coating composition used in the practice of the present invention. In general, the solvent can be any organic solvent and/or water. In one preferred embodiment, the solvent is a polar organic solvent. More preferably, the solvent is selected from polar aliphatic solvents or polar aromatic solvents. Still more preferably, the solvent is a ketone, ester, acetate, aprotic amide, aprotic sulfoxide, aprotic amine, or a combination of any of these. Examples of useful solvents include, without limitation, methyl ethyl ketone, methyl isobutyl ketone, m-amyl acetate, ethylene glycol butyl ether-acetate, propylene glycol monomethyl ether acetate, xylene, N-methylpyrrolidone, blends of aromatic hydrocarbons, and mixtures of these. In another preferred embodiment, the solvent is water or a mixture of water with small amounts of co-solvents.
The coating composition according to the invention is preferably utilized in an automotive or industrial high-gloss coating and/or as the clearcoat of an automotive composite color-plus-clear coating. High-gloss coatings as used herein are coatings having a 20xc2x0 gloss (ASTM D523) or a DOI (ASTM E430) of at least 80.
The coating composition may also be formulated as a pigmented coating, such as for a basecoat coating or a primer coating. In this case, the coating composition further includes a pigment or filler material. The pigment may be any organic or inorganic compounds or colored materials, metallic or other inorganic flake materials such as pearlescent mica flake pigments or metallic flake pigments such as aluminum flake, and other materials of kind that the art normally includes in such coatings. Examples of typical fillers are talc and barytes. Pigments and other insoluble particulate compounds such as fillers are usually used in the composition in an amount of 1% to 100%, based on the total solid weight of binder components (i.e., a pigment-to-binder ratio of 0.1 to 1).
Additional agents, for example surfactants, stabilizers, wetting agents, rheology control agents, dispersing agents, adhesion promoters, UV absorbers, hindered amine light stabilizers, etc. may be incorporated into the coating composition. While such additives are well-known in the prior art, the amount used must be controlled to avoid adversely affecting the coating characteristics.
Coating compositions can be coated on the article by any of a number of techniques well-known in the art. These include, for example, spray coating, dip coating, roll coating, curtain coating, and the like. For automotive body panels, spray coating is preferred.
When the coating composition according to the invention is used as the clearcoat of a composite color-plus-clear coating, the pigmented basecoat composition may any of a number of types well-known in the art, and does not require explanation in detail herein. Polymers known in the art to be useful in basecoat compositions include acrylics, vinyls, polyurethanes, polycarbonates, polyesters, alkyds, and polysiloxanes. Preferred polymers include acrylics and polyurethanes. In one preferred embodiment of the invention, the basecoat composition also utilizes a carbamate-functional acrylic polymer. Basecoat polymers may be thermoplastic, but are preferably crosslinkable and comprise one or more type of crosslinkable functional groups. Such groups include, for example, hydroxy, isocyanate, amine, epoxy, acrylate, vinyl, silane, and acetoacetate groups. These groups may be masked or blocked in such a way so that they are unblocked and available for the crosslinking reaction under the desired curing conditions, generally elevated temperatures. Useful crosslinkable functional groups include hydroxy, epoxy, acid, anhydride, silane, and acetoacetate groups. Preferred crosslinkable functional groups include hydroxy functional groups and amino functional groups.
Basecoat polymers may be self-crosslinkable, or may require a separate crosslinking agent that is reactive with the functional groups of the polymer. When the polymer comprises hydroxy functional groups, for example, the crosslinking agent may be an aminoplast resin, isocyanate and blocked isocyanates (including isocyanurates), and acid or anhydride functional crosslinking agents.
The coating compositions described herein are preferably subjected to conditions so as to cure the coating layer. Although various methods of curing may be used, heat-curing is preferred. Generally, heat curing is effected by exposing the coated article to elevated temperatures provided primarily by radiative heat sources. Curing temperatures will vary depending on the particular blocking groups used in the cross-linking agents, however they generally range between 90xc2x0 C. and 180xc2x0 C. The first compounds according to the present invention are preferably reactive even at relatively low cure temperatures. Thus, in a preferred embodiment, the cure temperature is preferably between 115xc2x0 C. and 150xc2x0 C., and more preferably at temperatures between 115xc2x0 C. and 140xc2x0 C. for a blocked acid catalyzed system. For an unblocked acid catalyzed system, the cure temperature is preferably between 80xc2x0 C. and 100xc2x0 C. The curing time will vary depending on the particular components used, and physical parameters such as the thickness of the layers, however, typical curing times range from 15 to 60 minutes, and preferably 15-25 minutes for blocked acid catalyzed systems and 10-20 minutes for unblocked acid catalyzed systems.
The invention is further described in the following example. The examples are merely illustrative and do not in any way limit the scope of the invention as described and claimed. All parts are parts by weight unless otherwise noted.